Inherent broadening, deconvolution

In liquids the interactions between neighboring molecules are considerably more complicated than in gases. The resultant broadening obliterates the fine line structure seen in gas spectra, leaving only broad band profiles. There are many possible contributors to this broadening. In some cases, adequate approximation is obtained by assuming that the band contour is established by collisions. Ramsay (1952) has noted that substitution of appropriate molecular density and collision diameter numbers in the collision broadening formula results in realistic band widths for certain liquid-phase systems. In such systems, the bands typically show an approximately Lorentzian profile. Approximate deconvolution of inherently broadened liquid-phase spectra may therefore be obtained on the basis of the assumption of Lorentzian shape (Kauppinen et al., 1981). 

It may have occurred to the reader that inherent line broadening could be removed by deconvolution. This appears especially attractive as a means of separating the various contributions. In the particular case of absorption spectra, however, it is not as straightforward as it at first appears. Referring to Eq. (9), we see that the various broadening-profile convolutions appear in the exponential ... 

Vibrational Raman band intensities and frequencies are also dependent on temperature, applied pressure, and the intrinsic microstructure of the material. These second-order parameters may be extracted from measured spectra. Both X-ray diffraction lines and Raman bands from polycrystalline materials show increased broadening as the microcrystallite grain sizes decrease. In fact, for the hexagonal phase of BN, bandwidths vary linearly with the reciprocal grain size (13). Inherent stress in thin films is manifested in vibrational line shifts. Based on pressure-dependent measurements of vibrational frequencies in bulk solids, inherent stress and stress inhomogeneity can be determined in thin films. Since localized stress can influence the optical and electronic properties of a thin film, it appears to be an important parameter in film characterization studies. Vibrational features also exhibit temperature-dependent frequency shifts. Therefore, an independent measurement of temperature is sometimes necessary to deconvolute these effects. Reference to Figure 1 shows that the molecular temperature of a material may be determined from the Stokes/anti-Stokes... 

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